Urea preparation



Feb. 4, 1964 BQNGARD 3,120,563

UREA PREPARATION Filed July 30, 1959 INVENTOR MATH IEU BON GARD BY MMfBQ EQM A TTORNEYS United States Patent 3,12%),563 UREA PREPARATION Mathieu Bongard, Geleen, Netherlands, assignor to Stamicarbon N.V., Heerlen, Netherlands Fiied .luly 30, 1959, Ser. No. 830,600 Claims priority, application Netherlands Aug. 8, 1953 3 Claims. (Cl. 260-655) The present invention relates to a process and apparatus for the preparation of urea from ammonia and carbon dioxide.

in this preparation, which is usually carried out by leading liquid ammonia and carbon dioxide into an autoclave in which the reaction mixture is kept at a pressure of at least 160 atm., and a temperature of ISO-200 (1., the reaction components first react to form ammonium carbamate. This is followed by the conversion of ammonium carbamate into urea and water. Such conversion is, however, not complete and, depending upon the temperature and pressure, an equilibrium is reached at which the degree of conversion is 4555%. This equilibrium may be shifted towards the formation of urea by adding to the urea synthesis more NH than the stoichiometric quantity (i.e. by applying during the synthesis a molar NH /CO ratio greater than 2).

However, the conversion of ammonium carbamate into urea and water carried out in the above mentioned way, is also far from complete. Thus, the melt leaving the synthesis autoclave still contains, in addition to water and urea, an amount of ammonium carbamate, and, if the reaction mixture is processed at an Nil /CO ratio 2, free NH After expansion of the synthesis melt to a suiiiciently low pressure, e.g., a pressure of one atm. gauge, a gaseous mixture of NH and CO is obtained in addition to an approximately 75% urea solution. Any ammonium carbamate still left in the solution can be completely removed by stripping the solution with a gas, e.g. air, in a stripping column.

As the immediate reintroduction of the NH CO -containing gas mixture obtained in the expansion and in the stripping process into the synthesis apparatus is accompanied by technical ditficulties on account of the formation of solid ammonium carbamate at temperatures below 150 C., it has for a long time been the practice merely to process the gas mixture, if necessary after absorption in water, to ammonium sulphate, ammonium nitrate, or ammonium chloride and soda (US. Patents 2,056,283 and 2,087,325). The disadvantage of this practice is that the urea production proper is coupled to a considerable production of another nitrogenous compound.

To eliminate this drawback, several proposals have been made, wherein the gas mixture is absorbed in such a small amount of water or other suitable solvent that the resulting concentrated solution, or suspension, can be pumped back into the synthesis apparatus without exercising too adverse an influence on the efiiciency of the conversion of ammonium carbamate into urea and water (US. Patents 1,898,093 and 2,116,881). However, these alternatives present certain problems. Thus, on the one hand, it is desirable to obtain a pure urea solution free of NH and CO and this is possible only if the urea melt is expanded to atmospheric or slightly higher pressure. On the other hand, it is also desirable to absorb all of the CO which has not been converted into urea in very little water, while forming an ammoniacal ammonium carbamate solution, and this is possible only if the absorption takes place at a relatively high pressure, at least 10 atm. gauge. To attain these objects, one has to use, besides the synthesis apparatus proper, a great deal of auxiliary equipment, viz. an expulsion column for the unconverted free NH a first carbamate still with condenser, and a second carbama-te still with condenser. These stills and condensers operate at diilerent pressure levels, and as a result considerable expenditure is also required for conduits between these pieces of equipment and for accessory expansion valves, pumps, and pressure safety devices. Moreover, operation and control are com plicated. The present invention has for its principal object the provision of a simplified process and apparatus, with attend-ant elimination of prior art problems.

According to the present invention, the process of preparing urea by reacting CO with excess NH at elevated temperature and pressure (e.g. to 220 C. at 150 to 400 atmospheres) involves expanding the urea synthesis reaction mixture, which contains urea, carbarnate and unrcacted Nil by reducing the pressure thereon to 10-45 atmospheres; removing any gas evolved as a result of said expansion; then decomposing the carbamate in the expanded reaction mixture by heating (e.g. between 110 and C.) at the reduced pressure to form additional urea while simultaneously passing an inert auxiliary gas, such as nitrogen, or air counter-currently through the mixture to strip NH and CO therefrom; thereafter supplying the resulting gaseous mixture of inert gas, CO and NH together with any gas evolved in the expansion step, to a cO -rernoving zone and passing this mixture of gases counter-currently through an ammonia solution containing little water (cg. not more than 15 to 30% water on the weight of the solution) whereby essentially all of the CO is removed by absorption and an ammoniacal ammoniurn carbamate solution is obtained, recycling this ammoniacal ammonium carbamate solution to the urea synthesis zone for the preparation of urea therefrom; removing the unabsorbed, essentially Co -free gaseous mixture of NH3 and inert gas from the CO -removing zone, cooling this unabsorbed gaseous mixture to condense the major portion of the NH therein to liquid NH refluxing a portion of the thus condensed N5 to the CO removing zone and supplying the remainder of the condensed NH to the urea synthesis zone for reaction with CO washing the gaseous mixture of NH and inert gas which remains after the Nil -condensation with water thereby obtaining an essentially NH -free inert gas and ammoniacal washing liquid which may have an ammonia concentration of, for example 50 to 90% by weight; recycling the NH -free inert gas to the stripping step and feeding the ammoniacal washing liquid to the CO -removal zone for removal of additional CO It will be recognized that the composition of the urea synthesis reaction mixture prior to its expansion will vary widely depending upon other operation conditions. Usually, however, this mixture will have approximately the following composition by weight: 20 to 35% urea; 20 to 35% ammonium carbamate; 20 to 35% NH and 10 to 20% water. As a result of the pressure-reduction from 8 to 20% by weight of the mixture, may be evolved a gas, mainly NH The amount of inert gas utilized in stripping NH and CO from the reaction mixture during carbamate decomposition may also be varied over a wide range. Sufficient inert gas should be used to effect essentially complete removal of the CO and NH at the operating temperature. The pressure-reduction and the stripping operation result in the formation of an aqueous urea solution containing from 55 to 75% urea in the usual case, and a gaseous mixture of, for example, 50 to 70% NH;, 15 to 30% CO 10% H 0 and to inert gas, all percentages being on a weight basis.

As indicated heretofore, the gaseous mixture obtained from the stripping operation and the expansion step is fed to the cO -removing zone for countercurrent contact with ammonia solution. Usually, from 50 to 200 parts gas per 100 parts of ammonia solution are sufficient to effect substantially complete removal of CO herein. The resulting ammoniacal ammonium carbamate solution usually has the following composition: to 20% ammonia, 60 to 75% ammonium carbamate and 15 to water and as indicated, is recycled to the urea synthesis zone for urea preparation. On the basis of 100 parts urea synthesis reaction mixture, this recycled portion will usually amount to from 20 to parts by weight.

The Co -removing or washing treatment is preferably carried out in such a way that the gas mixture containing NH CO inert gas and water vapor is first led into and through the ammoniacal ammonium carbamate solution to be discharged from the CO -removing zone, the solution collecting in the base of the Cog-washing zone. Thereafter, the gases which have not been absorbed in the solution flow in countercurrent relation through the ammonia solution containing little water. Thus, most of the CO is immediately condensed to an ammonium carbamate solution which is already in the base of the CO -Washing zone.

The CO -free gaseous mixture of NH and inert gas leaving the CO -removing zone may be cooled to between 25 to 65 C., or lower, to condense the major portion of the NH therein. Usually, from 75 to 95% by weight of the NH in the NH -inert gas mixture is condensed at this stage.

The amount of condensed NH refluxed to the CO removing zone depends on the quantity of CO to be condensed to ammonium carbamate. As an approximation, it may be said that the heat which is released in the condensation of gaseous CO to the ammonium carbamate solution has to be carried away by the refluxed liquid NH evaporating in the washing treatment for the CO removal, the temperature in the CO -removing zone being maintained at about 80 to 110 C., at the point where the CO -containing gas enters the zone and at about 30 to 70 C., at the exit. As an illustration, from 60 to 75 by weight of the condensed NH may be re fluxed to the CO -removing zone while the balance is fed to the urea synthesis zone.

The apparatus and method aspects of the present invention are further described below in conjunction with the accompanying diagrammatic drawing.

The reaction components NH and CO are fed to the urea synthesis apparatus 1 through the lines 18 and 19, respectively. The pressure in the urea autoclave is 150- 400 atmospheres. The resulting urea melt, which contains carbamate not yet converted into urea, dissolved NH and some water, is expanded to a pressure of 10-45 atmospheres through valve 2, after which the reaction product is led into a liquid-gas separator 4 through a heater 3.

From separator 4, a urea solution containing carbamate flows at the same pressure of 1045 atmospheres into the shipping column 5. The latter is provided with steam coils or the like so that the solution can be stripped in the column with inert gas fed into the base thereof through line 6.

From the base of column 5, a practically carbamatefree urea solution is discharged through line 7. This solution can be processed to urea crystals or urea prills in the usual way.

From the top of the column 5, a mixture of NH CO stripping gas, and some water flows away through line 10. Together with the gas spontaneously evolved in the expansion line 8, the mixture is led into the base of column 9, in which it comes into contact with liquid ammonia admitted into the top of the column through line 17, while water in the form of an NH OH solution is supplied to column 9 through line 16. As a result, a concentrated solution of ammonia and ammonium carbamate can be discharged from the base of column 9, this solution being fed back into the urea reactor 1 by means of pump 11.

From the top of column 9, CO -free NH -i-stripping gas escape, the NH being condensed in condenser 12. Part of the liquid NH is refluxed to column 9 and the remainder goes to a butter tank (not indicated in the drawing) from which NH is forced back into the urea autoclave 1 through line 18.

An uncondensed mixture of NH and inert gas is also discharged from condenser 12 and fed to a scrubber 13 where the NH is washed with water fed in through line 15. The resulting NH OI-I solution is discharged from the base of this scrubber 13 and led into the top of column 9 as washing liquid. The washed inert gases are discharged from the top of scrubber 15 and returned to the stripping column 5 through line 6 and pump 20. As the fresh NH; and CO; fed to the urea autoclave 1 always contain a certain percentage of inert matter, as a result of which the circulating quantity of inert material tends to increase, line 6 is provided with a discharge line 21 through which surplus inert material may be discharged.

The invention is further described, but not limited, by the following example:

Example Per hour 1,035 kg. of NH 614 kg. of CO comprising 11 kg. of inert matter, and a carbamate solution (composition: 452 kg. of NH 370 kg. of CO and 206 kg. of water), are fed into the reactor 1. This reaction mixture is brought to a pressure of 200 atm. gauge and a temperature of 180 C. as a result of which an hourly quantity of a synthesis melt consisting of 798 kg. of urea, 686 kg. of ammonium carbamate, 736 kg. of NH and 446 kg. of water is discharged from the autoclave. This melt is expanded to a pressure of 17 atm. gauge by means of valve 2 and is then led to the liquid vapor separator 4 through the heater 3 at a temperature of about 120 C. The liquid separated off at 4 is then stripped in the stripping column 5 with 123 kg. of nitrogen at a temperature of about C. From the base of the stripping column, 1189 kg. of urea solution, consisting of 798 kg. of urea, 335 kg. of water, and 36 kg. of NH +CO is discharged.

The gases discharged from the stripping column 5 join the gases escaping from the liquid-gas separator 3 at the base of washing column 9. The resulting gas mixture, which consists of 1016 kg. of NH 370 kg. of CO 91 kg. of H 0 and 134 kg. of inert gas, is washed in countercurrent with liquid ammonia containing water, in the washing column 9, the temperature at the base and top of the column being kept at about 90 C. and about 50 C., respectively. Some of the NH escaping from the washing column 9 is condensed by cooling in condenser 12 and partly refluxed into washing column 9, the remainder being returned to the urea synthesis. The gas mixture escaping from condenser 12, consisting of 134 kg. of inert gas and 134 kg. of NH is washed with kg. or" water in scrubber 13. In this washing step, 249 kg. of NI-I OH solution are obtained and this is also refluxed into washing column 9. From the base of the washing column 9, a carbamate solution consisting of 452 kg. of NH 370 kg. of CO and 206 kg. of water is discharged and pumped back into the urea reactor 1. 11 kg. of inert material is discharged through line 21, the

remainder being led back into the base of the stripping column 5.

In this way, 60.3% of the CO is converted into urea at a molar NH /CO ratio of 3.96 and a molar H 0/CO ratio of 0.52, practically all of the NH and CO which has not been converted into urea being returned to the urea reactor.

The method according to the invention has the advantage that the expulsion of the carbamate from the carbamate-containing urea melt delivered by the urea reactor, and the subsequent condensation to a concentrated solution of ammonia and ammonium carbamate, are not effected in a number of different pressure stages, but in one stage, in which by the effect of the stripping gas the partial vapor pressure of the NH and CO over the urea solution to be liberated from carbamate gradually decreases, While the NH and CO released in this process are condensed at a relatively high pressure in ammonia containing water. On account of this relatively high pressure, it is possible to obtain a concentrated carbamate solution, which can be recycled to the urea synthesis proper in reactor 1 without a substantial decrease in efli ciency. Because of the absence of different pressure stages in the recirculation apparatus, the number of columns is reduced to three, viz. the stripping'column 5, column 9 for condensing NH and CO to ammonium carbamate solution, and a washing column 13 for washing NH from the inert gases. Moreover, only a few expansion valves are necessary, viz. valve 2, valve 14 in the urea discharge line 7 and a valve in the discharge line 21, and only three simple pumps are required, viz. a pump 11 for forcing the resulting ammonium carbamate solution into the urea reactor, pump 20 for keeping the inert auxiliary gas circulating, and a pump (which does not appear in the drawing) for feeding Water to the pressurized scrubber 13 through line 15. Because a uniform pressure is maintained throughout the apparatus, control and operation are simple, and the prevention of operating problems is much easier, so that a highly reliable recirculating apparatus is obtained.

It will be apparent from the foregoing that the apparatus of the invention comprises the following: a reactor for preparing a reaction product containing urea, water, carbamate and NH means for withdrawing the reaction product from the reactor; means for reducing the pressure on the reaction product; a carbamate-decomposing and gas stripping vessel; means for feeding the reaction prodnet after pressure reduction into one end of said vessel; means for heating said vessel to decompose the carbamate therein; means for passing an auxiliary inert gas through said vessel countercurrently to said reaction product to strip NH and CO therefrom; a CO -removing tower; means for withdrawing a gaseous mixture of inert gas and stripped NH and CO from the top of the vessel and for feeding this gaseous mixture into the base of the CO removing tower; means for feeding ammonia washing liquid into the top of the tower in countercurrent contact with the gaseous mixture whereby CO is removed from the gaseous mixture; means for collecting an ammoniacal ammonium carbamate solution in the base of the tower; means for withdrawing this solution from the base of the tower and recycling the same to the reactor; means for removing essentially Co -free gas from the top of the tower; means for cooling this CO -free gas to condense NH therein; means for feeding a portion of the condensed NH into the top of the Co -removing tower as ammonia washing liquid; means for feeding the balance of the condensed NH to the reactor; a second tower; means for withdrawing uncondensed gases from said cooling tower and feeding same into the bottom of the second tower; means for supplying wash water into the top of the second tower for countercurrent washing contact with the uncondensed gases, means for collecting the resulting liquid in the base of the tower; means for recycling this liquid to the top of the CO -removing tower; and means for recycling the washed gas from the second tower to the decomposing and stripping vessel.

It will be appreciated that various modifications may be made in the invention as described above. Accordingly, the scope of the invention is defined in the following claims wherein, what is claimed is:

l. in a process for preparing urea from NH and CO using excess NI-i and wherein NH and CO are reacted in a urea synthesis zone at elevated temperature and pressure to form a liquid reaction mixture including ammonium carbamate and the carbamate in said reaction mixture is thereafter decomposed to urea and NH and CO not converted to urea are recycled for further reaction, the improvements which comp-rise expanding the liquid carbamate-containing reaction mixture by reducing the pressure thereon to a pressure of 10-45 atmospheres; then decomposing the carbamate in said liquid reaction mixture to form urea by heating said mixture at said reduced pressure and simultaneously passing an auxiliary gas inert to said reaction mixture counter-currently through said mixture to strip NH and CO therefrom, thereafter supplying the resulting gaseous mixture containing inert gas, CO and NH together with any gas evolved in said expansion step, to a CO -removing zone and passing said mixture of gases counter-currently through an ammonia solution containing little water where-by CO is removed from said gases by absorption and an ammoniacal ammonium carbarnate solution is obtained, recycling said ammoniacal ammonium carbamate solution to said urea synthesis zone, removing the unabsorbed, essentially CO -free gaseo-us mixture of NH and inert gas from said CO- -removing zone, cooling said unabsorbed gaseous mixture to condense the major portion of N-H therein to liquid NH refluxing a portion of the thus condensed NH to the cO -removing zone and supplying the remainder of said condensed NR to the urea synthesis zone for reaction with CO Washing the gaseous mixture of NH, and inert gas which remains after said condensation with water thereby obtaining an essentially NH -free inert gas and 'ammoniacal washing liquid, recycling the NH -free inert gas to said stripping step and feeding the ammoniacal washing liquid to the CO removal Zone for removal of additional C0 2. The process of claim 1 wherein a uniform pressure is maintained through the various steps of said process.

3. Apparatus for preparing urea by reaction of NH and CO comprising a reactor for preparing a reaction product containing urea, water, carbamate and NH means for withdrawing the reaction product from the reactor; means for reducing the pressure on the reaction product; a carbamate-decomposing and gas-stripping vessel; means for feeding the reaction product after pressure reduction into one end of said vessel; means for heating said vessel to decompose the carbamate therein; means for passing an auxiliary inert gas through said vessel countercurrently to said reaction product to strip Nil-l and CO therefrom; a CO removing tower; means for withdrawing a gaseous mixture of inert 'gas and stripped NFL, and CO from the top of the vessel and for feeding this gaseous mixture into the base of the CO' -removing tower; means for feeding ammonia washing liquid into the top of the tower in countercurrent contact with the gaseous mixture whereby CO is removed from the gaseous mixture; means for collecting an ammoniacal ammonium carbamate solution in the base of the tower; means for withdrawing this solution from the base of the tower and recycling the same to the reactor; means for removing essentially CO -free gas from the top of the tower; means for cooling this CO free gas to condense N-H therein; means for feeding a portion of the condensed NH into the top of the CO rernoving tower, as ammonia washing liquid; means for feeding the balance of the condensed NH to the reactor; a second tower; means for withdrawing uncondensed gases from said cooling tower and feeding same into the bottom of the second tower; means for supplying wash water into 2,2611 33 Porter Dec. 23, 1941 the top of the said tower for countercurrent Washing 2,632,711 White Mar. 2-1, 1953 contact with the uncondensed gases; means for collecting 2,337,574 Hiram et at, Sew. 24, 1957 the resulting liquid in the base of the tower; means for 2 359 350 B m b S 2 1953 recycling this liquid to the top of the CO -removing tower; 5 and means for recycling the washed gas from the second OTHER REFERENCES we th decom OSll and srip in vessel. I to e p 1 g L p D Tonn: Chemical Engineering, volume 62 (October References Cited in the file of thls patent 195 Pagas 136499 UNITED STATES PATENTS 10 Harding: Ammonia Manufacture and Uses (1959), 1,784,074 Pauling Dec. 9, 1930 pages 25-27. 

1. IN THE PROCESS FOR PREPARING UREA FROM NH3 AND CO2 USING EXCESS NH3 AND WHEREIN NH3 AND CO2 ARE REACTED IN A UREA SYNTHESIS ZONE AT ELEVATED TEMPERATURE AND PRESSURE TO FORM A LIQUID REACTION MIXTURE INCLUDING AMMONIUM CARBAMATE AND THE CARBAMATE IN SAID REACTION MIXTURE IS THEREAFTER DECOMPOSED TO UREA AND NH3 AND CO2 NOT CONVERTED TO UREA ARE RECYCLED FOR FURTHER REACTION, THE IMPROVEMENTS WHICH COMPRISE EXPANDING THE LIQUID CARBAMATE-CONTAINING REACTION MIXTURE BY REDUCING THE PRESSURE THEREON TO A PRESSURE OF 10-45 ATMOSPHERES; THEN DECOMPOSING THE CARBAMATE IN SAID LIQUID REACTION MIXTURE TO FORM UREA BY HEATING SAID MIXTURE AT SAID REDUCED PRESSURE AND SIMULTANEOUSLY PASSING AN AUXILARY GAS INERT TO SAID REACTION MIXTURE COUNTER-CURRENTLY THROUGH SAID MIXTURE TO STRIP NH3 AND CO2 THEREFROM, THEREAFTER SUPPLYING THE RESULTING GASEOUS MIXTURE CONTAINING INERT GAS, CO2 AND NH3 TOGETHER WITH ANY GAS EVOLVED IN SAID EXPANSION STEP, TO A CO2-REMOVING ZONE AND PASSING MIXTURE OF GASES COUNTER-CURRENTLY THROUGH AN AMMONIA SOLUTION CONTAINING LITTLE WATER WHEREBY CO2 IS REMOVED FROM SAID GASES BY ABSORPTION AND AN AMMONIACAL AMMONIUM CARBAMATE SOLUTION IS OBTGAINED, RECYCLING SAID AMMONIACAL AMMONIUM CARBAMATE SOLUTION TO SAID UREA SYNTHESIS ZONE, REMOVING THE UNABSORBED, ESSENTIALLY CO2-FREE GASEOUS MIXTURE OF NH3 AND INERT GAS FROM SAID CO2-REMOVING ZONE, COOLING SAID UNABSORBED GASEOUS MIXTURE TO CONDENSE THE MAJOR PORTION OF NH3 THEREIN TO LIQUID NH3, REFLUXING A PORTION OF THE THUS CONDENSED NH3 TO THE CO2-REMOVING ZONE AND SUPPLYING THE REMAINDER OF SAID CONDENSED NH3 TO THE UREA SYNTHESIS ZONE FOR REACTION WITH CO2, WASHING THE GASEOUS MIXTURE OF NH3 AND INERT GAS WHICH REMAINS AFTER SAID CONDENSATION WITH WATER THEREBY OBTAINING AN ESSENTIALLY NH3-FREE INERT GAS AND AMMONIACAL WASHING LIQUID, RECYCLING THE NH3-FREE INERT GAS TO SAID STRIPPING STEP AND FEEDING THE AMMONIACAL WASHING LIQUID TO THE CO2 REMOVAL ZONE FOR REMOVAL OF ADDITIONAL CO2. 